CN115724604A - A kind of preparation method of composite antibacterial gel material - Google Patents

Abstract

The invention discloses a preparation method of a composite antibacterial gelling material, comprising the following steps: (1) dissolving zinc salt in water to obtain a zinc-containing solution, dissolving imidazole in water to obtain an imidazole solution, and pouring the zinc salt solution into the imidazole solution , to obtain a mixed solution; the mixed solution is left to stand and then suction filtered, washed after suction filtration, dried and ground after washing to obtain a ZIF‑8 carrier; (2) dissolving zinc salt in water to obtain a zinc salt solution, and ZIF‑8 The carrier is immersed in a zinc salt solution, suction filtered after dipping, washed after suction filtration, dried after washing, and roasted at 550 ° C for 4 to 5 hours after drying to obtain a nano zinc oxide material; (3) the nano zinc oxide material obtained in step (2) The zinc oxide material is mixed with light-burned magnesium oxide to obtain a mixed powder; (4) magnesium sulfate heptahydrate crystals are dissolved in water to obtain a magnesium sulfate solution, and the mixed powder is added to the magnesium sulfate solution, and stirred to obtain a composite antibacterial gelling material.

Description

A kind of preparation method of composite antibacterial gel material

technical field

The invention relates to a preparation method of a composite antibacterial gelling material.

Background technique

As a new type of building material, magnesium oxysulfate cementitious material is an air-hardening cementitious material formed by hydration reaction of light-burned magnesium oxide, magnesium sulfate heptahydrate solution and other additives. It has the advantages of low heat resistance, fire resistance and high temperature resistance, and is often used in decorative materials, prefabricated houses, fire door panels, transportation facilities and other fields.

The pH value of newly poured magnesium oxysulfide cement is generally between 10 and 12, which is alkaline. However, due to the poor antibacterial performance of most magnesium oxysulfide structural materials and the lack of protection in actual use, direct contact with air causes Various bacteria and microorganisms in the air adhere to its surface, and at the same time, the discharge of various garbage and sewage in walls and pipes leads to the gradual deposition of organic and inorganic suspended solids on the surface of magnesium oxysulfide structural materials, breeding a large number of bacteria, and transforming sulfate form H ₂ S, and react with O ₂ to generate H ₂ SO ₄ , under the action of H ₂ SO ₄ , the magnesium oxysulfide cement on the surface will generate a layer of loose white expansive product gypsum and ettringite, making magnesium oxysulfide The cement structure suffered damage.

Contents of the invention

Purpose of the invention: The purpose of the present invention is to provide a method for preparing a composite antibacterial gelling material, which has excellent antibacterial properties.

Technical solution: The preparation method of the composite antibacterial gelling material of the present invention comprises the following steps:

(1) Dissolve zinc salt in water to obtain a zinc-containing solution, dissolve imidazole in water to obtain an imidazole solution, slowly pour the zinc salt solution into the imidazole solution to obtain a mixed solution, and in the mixed solution, the molar ratio of Zn ²⁺ to imidazole The ratio is 1 to 4:10; the mixed solution is magnetically stirred at room temperature and left to stand, and the solution after standing is subjected to suction filtration, washed after the suction filtration is completed, then dried and ground to obtain the ZIF-8 carrier;

(2) Take zinc salt and dissolve it in water to obtain zinc salt solution, immerse the ZIF-8 carrier in the zinc salt solution, the mass ratio of Zn ²⁺ to ZIF-8 carrier is 0.01～0.05:1, soak for 24～48h, the The impregnated solution is subjected to suction filtration, washed after suction filtration, dried after washing, ground, and then roasted at 550°C for 4 to 5 hours to obtain nano-zinc oxide materials; compared to direct calcination of the ZIF-8 carrier, the Calcination after dipping in the solution can effectively increase the active sites of nano-zinc oxide materials. On the one hand, impregnation can increase the content of zinc oxide nanoparticles. On the other hand, the ZIF-8 carrier has a three-dimensional network structure and has multiple channels. After dipping, it can Make zinc ions evenly distributed on the organic framework, so that zinc oxide nanoparticles are evenly distributed inside and outside the pores of the carbon carrier;

(3) Mix the nano-zinc oxide material obtained in step (2) with light-burned magnesia to obtain a mixed powder; The dispersion uniformity of zinc material in magnesium sulfate solution;

(4) Dissolve magnesium sulfate heptahydrate crystals in water to obtain a magnesium sulfate solution, add a mixed powder of nano-zinc oxide material and light-burned magnesium oxide to the magnesium sulfate solution, and stir to form a slurry with uniform viscosity, which is a composite antibacterial gelling material.

Wherein, in step (1) and step (2), the zinc salt is zinc nitrate hexahydrate, zinc acetate, zinc chloride or zinc sulfate; the imidazole is 2-methylimidazole.

Wherein, in step (1), the drying temperature is not lower than 60° C., and the drying time is 12 to 14 hours.

Wherein, in step (2), the soaking time is 24-48 hours; the drying temperature is not lower than 110° C., and the drying time is 5-6 hours.

Wherein, in step (2), the nano-zinc oxide material uses porous carbon as a carrier, and zinc oxide nanoparticles are loaded on the carrier; the particle size of the nano-zinc oxide material is 50-80 nm.

Wherein, in the step (3), the mixing mass ratio of the nano-zinc oxide material to the light-burned magnesium oxide is 1-2:100. Adding too much nano-zinc oxide material will reduce the strength of the cementitious material after hardening.

Wherein, in step (4), the molar ratio of light-burned magnesium oxide, magnesium sulfate heptahydrate crystals and water is 8-12:1:12-20.

Among them, the mass proportion of active magnesia in light-burned magnesia is not less than 65%

When the present invention prepares nanometer zinc oxide material, ZIF-8 is used as carrier, and in calcining process, organic skeleton overflows with CO ₂ and H ₂ O (g) or other gas forms, thereby produces porous structure material, simultaneously metal ion (zinc ) is converted into metal oxide (zinc oxide) in high temperature air and attached to the surface of the porous material to form a nanoporous metal oxide; at the same time, the zinc ions adsorbed on the surface of the organic framework by the impregnation method are also oxidized into metal oxide and attached to the porous material. On the surface of the material, the overflowing gas can effectively avoid the agglomeration of metal oxides on the surface of the material; the nano-zinc oxide material prepared by the method of the present invention can effectively avoid the agglomeration of metal ions, which is beneficial to the dispersion of metal oxides on the carrier, thereby improving the nano Antimicrobial activity of zinc oxide materials.

In the present invention, the nano-zinc oxide material is uniformly mixed with light-burned magnesium oxide, and then added to the magnesium sulfate solution, so that the nano-zinc oxide material can be uniformly dispersed in the slurry, and the inside and surface of the slurry have nano-zinc oxide material. distribution, so as to give full play to the antibacterial and antibacterial effects of nano-zinc oxide materials; nano-zinc oxide can interact with the cell wall on the surface of bacteria, destroy the cell wall of bacteria, and cause the content to be released to kill bacteria; at the same time, nano-zinc oxide can be used in water Zinc ions are continuously released in the medium. Zinc ions will enter the cell membrane and destroy the cell membrane. When they react with certain groups of proteins in the cell, they will destroy the spatial structure of the bacteria and the protein in the cell, resulting in the inactivation of the protease in the cell and then killing the bacteria. After the destruction, the zinc ions will be freed from the bacteria, and the sterilization process will be repeated.

Beneficial effects: Compared with the prior art, the present invention has the following significant advantages: the composite antibacterial gel material prepared by the method of the present invention uniformly disperses zinc oxide with high active sites on the surface of the porous carbon carrier to make it possess High antibacterial reactivity, so that the composite antibacterial gel material has a good antibacterial and antibacterial effect, and realizes the wide application of the composite antibacterial gel material in the field of building materials.

Description of drawings

Fig. 1 is the SEM figure of nano zinc oxide material in embodiment 1;

Fig. 2 is a flow chart of the preparation of the composite antibacterial gelling material of the present invention.

Detailed ways

Example 1

The preparation method of composite antibacterial gelling material of the present invention, comprises the steps:

(1) Dissolve 2.9749g Zn(NO ₃ ) ₂ ·6H ₂ O in 40mL water to obtain a zinc nitrate solution, dissolve 3.284g 2-methylimidazole in 40mL water to obtain an imidazole solution, slowly pour the zinc nitrate solution into the imidazole solution , stirred at 25°C for 2h, the rotating speed of the magnetic stirrer was 600r/min, and stood still for 10min. The solution after standing was subjected to suction filtration. Dry under vacuum for 12h, grind to obtain ZIF-8 carrier;

(2) Dissolve 0.03g Zn(NO ₃ ) ₂ ·6H ₂ O in 20mL of water to obtain a zinc nitrate solution, then put 1g of ZIF-8 carrier into the zinc nitrate solution, let it stand for 36h, and carry out Suction filtration, wash with water and absolute ethanol three times respectively after suction filtration, then vacuum dry at 110°C for 5 hours, grind, and finally calcinate at 550°C for 4 hours to obtain nano-zinc oxide materials; the filter membrane used in suction filtration It is a microporous membrane with a pore size of 0.45 μm;

(3) the nano-zinc oxide material obtained in step (2) is mixed with light-burned magnesium oxide to obtain mixed powder;

(4) Dissolve magnesium sulfate heptahydrate crystals in water to obtain a magnesium sulfate solution, add a mixed powder of nano-zinc oxide material and light-burned magnesium oxide to the magnesium sulfate solution, and stir to form a slurry (that is, a composite antibacterial gelling material) Wherein, the mixed molar ratio of light-burned magnesium oxide, magnesium sulfate heptahydrate crystal and water is 8:1:12; the content of active magnesium oxide in the light-burned magnesium oxide powder is 65%, and the amount of nano-zinc oxide material is light-burned oxidized 2% of the mass of magnesium powder.

When it needs to be used, inject the slurry into the mold, demould after molding and harden in the air.

It can be seen from Fig. 1 that the particle size of the nano-zinc oxide material prepared in Example 1 is nanoscale, and it is a loaded composite material.

Example 2

The preparation method of composite antibacterial gelling material of the present invention, comprises the steps:

(1) Dissolve 2.9749g Zn(NO ₃ ) ₂ ·6H ₂ O in 40mL water to obtain a zinc nitrate solution, dissolve 3.284g 2-methylimidazole in 40mL water to obtain an imidazole solution, slowly pour the zinc nitrate solution into the imidazole solution , stirred at 25°C for 2h, the rotating speed of the magnetic stirrer was 600r/min, and stood still for 10min. The solution after standing was subjected to suction filtration. Dry under vacuum for 12h, grind to obtain ZIF-8 carrier;

(2) Dissolve 0.03g Zn(NO ₃ ) ₂ ·6H ₂ O in 20mL of water to obtain a zinc nitrate solution, then put 1g of ZIF-8 carrier into the zinc nitrate solution, let it stand for 36h, and carry out Suction filtration, wash with water and absolute ethanol three times respectively after suction filtration, then vacuum dry at 110°C for 5 hours, grind, and finally calcinate at 550°C for 4 hours to obtain nano-zinc oxide materials; the filter membrane used in suction filtration It is a microporous membrane with a pore size of 0.45 μm;

(3) the nano-zinc oxide material obtained in step (2) is mixed with light-burned magnesium oxide to obtain mixed powder;

(4) Dissolve magnesium sulfate heptahydrate crystals in water to obtain a magnesium sulfate solution, add a mixed powder of nano-zinc oxide material and light-burned magnesium oxide to the magnesium sulfate solution, and stir to form a slurry (that is, a composite antibacterial gelling material) Wherein, the mixed molar ratio of light-burned magnesium oxide, magnesium sulfate heptahydrate crystal and water is 10:1:12; the content of active magnesium oxide in the light-burned magnesium oxide powder is 65%, and the amount of nano-zinc oxide material is light-burned oxidized 1% of the mass of magnesium powder.

When it needs to be used, inject the slurry into the mold, demould after molding and harden in the air.

Comparative example 1

A preparation method of a composite antibacterial gel material, comprising the steps of:

(1) Dissolve 2.9749g Zn(NO ₃ ) ₂ ·6H ₂ O in 40mL water to obtain a zinc nitrate solution, dissolve 3.284g 2-methylimidazole in 40mL water to obtain an imidazole solution, slowly pour the zinc nitrate solution into the imidazole solution , stirred at 25°C for 2h, the rotating speed of the magnetic stirrer was 600r/min, and stood still for 10min. The solution after standing was subjected to suction filtration. Dry under vacuum for 12h, grind to obtain ZIF-8 carrier;

(2) Take 1g of ZIF-8 carrier and calcinate directly at 550°C for 4h to obtain nano-zinc oxide material;

(3) the nano-zinc oxide material obtained in step (2) is mixed with light-burned magnesium oxide to obtain mixed powder;

(4) Dissolve magnesium sulfate heptahydrate crystals in water to obtain a magnesium sulfate solution, add a mixed powder of nano-zinc oxide material and light-burned magnesium oxide to the magnesium sulfate solution, and stir to form a slurry (that is, a composite antibacterial gelling material) Wherein, the mixed molar ratio of light-burned magnesium oxide, magnesium sulfate heptahydrate crystal and water is 8:1:12; the content of active magnesium oxide in the light-burned magnesium oxide powder is 65%, and the amount of nano-zinc oxide material is light-burned oxidized 2% of the mass of magnesium powder.

When it needs to be used, inject the slurry into the mold, demould after molding and harden in the air.

Comparative example 2

Get magnesium sulfate heptahydrate crystal and be dissolved in water to obtain magnesium sulfate solution, add light-burned magnesium oxide to the magnesium sulfate solution and stir to form slurry (being gelling material); Wherein, light-burned magnesium oxide, magnesium sulfate heptahydrate crystal and The mixing molar ratio of water is 8:1:12; the content of active magnesium oxide in light-burned magnesium oxide powder is 65%.

When it needs to be used, inject the slurry into the mold, demould after molding and harden in the air.

Comparative example 3

A preparation method of a composite antibacterial gel material, comprising the steps of:

(1) Dissolve 2.9749g Zn(NO ₃ ) ₂ ·6H ₂ O in 40mL water to obtain a zinc nitrate solution, dissolve 3.284g 2-methylimidazole in 40mL water to obtain an imidazole solution, slowly pour the zinc nitrate solution into the imidazole solution , stirred at 25°C for 2h, the rotating speed of the magnetic stirrer was 600r/min, and stood still for 10min. The solution after standing was subjected to suction filtration. Dry under vacuum for 12h, grind to obtain ZIF-8 carrier;

(2) Dissolve 0.03g Zn(NO ₃ ) ₂ ·6H ₂ O in 20mL of water to obtain a zinc nitrate solution, then put 1g of ZIF-8 carrier into the zinc nitrate solution, let it stand for 36h, and carry out Suction filtration, wash with water and absolute ethanol three times respectively after suction filtration, then vacuum dry at 110°C for 5 hours, grind, and finally calcinate at 550°C for 4 hours to obtain nano-zinc oxide materials; the filter membrane used in suction filtration It is a microporous membrane with a pore size of 0.45 μm;

(3) the nano-zinc oxide material obtained in step (2) is mixed with light-burned magnesium oxide to obtain mixed powder;

(4) Dissolve magnesium sulfate heptahydrate crystals in water to obtain a magnesium sulfate solution, add a mixed powder of nano-zinc oxide material and light-burned magnesium oxide to the magnesium sulfate solution, and stir to form a slurry (that is, a composite antibacterial gelling material) Wherein, the mixed molar ratio of light-burned magnesium oxide, magnesium sulfate heptahydrate crystal and water is 8:1:12; the content of active magnesium oxide in the light-burned magnesium oxide powder is 65%, and the amount of nano-zinc oxide material is light-burned oxidized 0.1% of the mass of magnesium powder.

When it needs to be used, inject the slurry into the mold, demould after molding and harden in the air.

Escherichia coli with an initial concentration of 1.1×10 ⁶ cfu/mL were respectively inoculated on the surfaces of the cured cementitious materials in Examples 1-2 and Comparative Examples 1-3 to test the bactericidal performance. The experimental results are shown in Table 1. E. coli The bacteria were cultured on the material surface for 4 hours, and the inoculum concentration of Escherichia coli was 1.1×10 ⁶ cfu/ml.

Table 1 Escherichia coli antibacterial performance test of antibacterial gel material

It can be seen from Table 1 that zinc ions are loaded on the ZIF-8 carrier by the impregnation method, and then the nano-zinc oxide material with a porous carbon carrier is prepared, and the application in the magnesium oxysulfide gelling material can fully improve the bactericidal performance of the gelling material .

Claims (8)

1. The preparation method of the composite antibacterial cementing material is characterized by comprising the following steps:

(1) Dissolving zinc salt in water to obtain zinc-containing solution, dissolving imidazole in water to obtain imidazole solution, pouring zinc salt solution into imidazole solution to obtain mixed solution, and adding Zn into the mixed solution ²⁺ The molar ratio of the imidazole to the imidazole is 1-4; standing the mixed solution, performing suction filtration, washing after suction filtration, drying after washing, and grinding to obtain a ZIF-8 carrier;

(2) Dissolving zinc salt in water to obtain zinc salt solution, soaking ZIF-8 carrier in the zinc salt solution, and adding Zn ²⁺ The mass ratio of the zinc oxide to the ZIF-8 carrier is 0.01-0.05, the zinc oxide is dipped, filtered, washed, dried and roasted at 550 ℃ for 4-5 hours to obtain a nano zinc oxide material;

(3) Mixing the nano zinc oxide material obtained in the step (2) with light-burned magnesium oxide to obtain mixed powder;

(4) Dissolving magnesium sulfate heptahydrate crystals in water to obtain a magnesium sulfate solution, adding the mixed powder into the magnesium sulfate solution, and stirring to obtain the composite antibacterial cementing material.

2. The preparation method of the composite antibacterial cementing material according to claim 1, characterized in that: in the step (1) and the step (2), the zinc salt is zinc nitrate hexahydrate, zinc acetate, zinc chloride or zinc sulfate; the imidazole is 2-methylimidazole.

3. The preparation method of the composite antibacterial cementing material according to claim 1, characterized in that: in the step (1), the drying temperature is not lower than 60 ℃, and the drying time is 12-14 h.

4. The preparation method of the composite antibacterial cementing material according to claim 1, characterized in that: in the step (2), the dipping time is 24-48 h; the drying temperature is not lower than 110 ℃, and the drying time is 5-6 h.

5. The preparation method of the composite antibacterial cementing material according to claim 1, characterized in that: in the step (2), the nano zinc oxide material takes porous carbon as a carrier, and zinc oxide nano particles are loaded on the carrier; the particle size of the nano zinc oxide material is 50-80 nm.

6. The preparation method of the composite antibacterial cementing material according to claim 1, characterized in that: in the step (3), the mixing mass ratio of the nano zinc oxide material to the light-burned magnesium oxide is 1-2: 100.

7. the preparation method of the composite antibacterial cementing material according to claim 1, characterized in that: in the step (4), the mol ratio of the light calcined magnesium oxide to the magnesium sulfate heptahydrate crystal to water is 8-12: 1:12 to 20.

8. The preparation method of the composite antibacterial cementing material according to claim 7, characterized in that: the weight percentage of the active magnesium oxide in the light-burned magnesium oxide is not less than 65 percent.

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